EP0106206B1 - Epoxy resin composition - Google Patents

Epoxy resin composition Download PDF

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Publication number
EP0106206B1
EP0106206B1 EP83109409A EP83109409A EP0106206B1 EP 0106206 B1 EP0106206 B1 EP 0106206B1 EP 83109409 A EP83109409 A EP 83109409A EP 83109409 A EP83109409 A EP 83109409A EP 0106206 B1 EP0106206 B1 EP 0106206B1
Authority
EP
European Patent Office
Prior art keywords
epoxy resin
anhydride
component
weight
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP83109409A
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German (de)
English (en)
French (fr)
Other versions
EP0106206A1 (en
Inventor
Toru Kikuchi
Takayuki Saito
Akihiro Kobayashi
Hitoshi Goto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
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Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Publication of EP0106206A1 publication Critical patent/EP0106206A1/en
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Publication of EP0106206B1 publication Critical patent/EP0106206B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/625—Hydroxyacids

Definitions

  • This invention relates to an epoxy resin composition containing a polycarboxylic acid anhydride and 4-ketopimelic acid dilactone as curing agent.
  • Epoxy resins are used as electrically insulating materials, for example, for embedding or encapsulating various electronic and electric parts. They are widely used also as adhesives because they have good adhesion to hard surfaces of metals and glass.
  • the epoxy resins are used for embedding or adhesion, they are different in thermal expansion coefficient from materials to be embedded or adhered such as metals and the like, and therefore when such a system is placed in a heat cycle of heating and cooling, a large stress is caused by internal strain and the system is eventually destroyed.
  • a method of imparting flexibility to a cured epoxy resin there are, for example, a method in which a flexible epoxy resin such as a diglycidyl ester of dimeter acid, a bisphenol side chain type epoxy resin or a diglycidyl ether of polyoxyalkylene glycol is incorporated; a method in which a polyamide obtained from a dimer acid and an excess of diamine or dodecenylsuccinic anhydride is used as a curing agent; and a method in which a flexibility-imparting agent such as a polyester having a hydroxyl group at an end or a polyoxyalkylene glycol is incorporated.
  • these methods have been disadvantageous in that mechanical properties such as hardness and tensile strength of the resulting cured products are greatly deteriorated.
  • alicyclic or aromatic polycarboxylic acid anhydrides are often used, but they cannot impart flexibility to a cured product.
  • 4-ketopimelic acid dtlactone is crystals having a melting point of 65°C and therefore when it alone is used as a curing agent for an epoxy resin, it should be heated to its melting point or higher in order to mix it homogeneously with the epoxy resin, so that the pot life is short.
  • the object of the present invention is to provide an epoxy resin composition which can give a cured epoxy resin having good elongation or extensibility and high tensile strength without lowering the hardness.
  • an epoxy resin composition comprising
  • This 4-ketopimelic acid dilactone can be produced by processes described in Annalen der Chemie Vol. 253, p. 206 (1890) and German Offenlegungsschrift No. 2,136,886, wherein 4-ketopimelic acid dilactone is obtained by heating succinic anhydride at a high temperature in the presence of an alkali catalyst to proceed bimolecular decarboxylation condensation.
  • this 4-ketopimelic acid dilactone alone is used as an agent for curing an epoxy resin, the volume shrinkage during cure reaction is slight, but the resulting cured product is very low in hardness (Barcol hardness) and very easy to be injured and hence is of no practice use.
  • the above-mentioned alicyclic polycarboxylic acid anhydride is preferably one that is liquid at ordinary temperatures.
  • alicyclic polycarboxylic acid anhydrides are used alone or in admixture of the two.
  • alicyclic polycarboxylic acid anhydrides are used alone or in admixture of the two.
  • eutectic mixtures of hexahydrophthalic anhydride and tetrahydrophthalic anhydride are also eutectic mixtures of hexahydrophthalic anhydride and tetrahydrophthalic anhydride.
  • the above-mentioned alicyclic polycarboxylic acid anhydrides which are liquid at ordinary temperatures are mixtures of their stereoisomers or structural isomers.
  • the mixtures of the stereoisomers are mixtures of cis and trans forms of the above-mentioned alicyclic polycarboxylic acid anhydrides, and can be obtained by mainly heating the individual cis forms in the presence or absence of a basic catalyst or by hydrogenating methyltetrahydrophthalic anhydride.
  • the former/the latter is preferaby 7/3 to 3/7, particularly preferably 6/4 to 4/6.
  • the mixtures of the structural isomers can be obtained by mainly using methyltetrahydrophthalic anhydride (in particular, 3- or 4-methyl-Ll4-tetrahydrophthalic anhydride) as a starting material and heating it in the presence of an acidic catalyst or a noble metal catalyst.
  • the mixture of the structure isomers comprises structural isomers which are different from one another in the position of double bond in the six-membered ring.
  • the aforesaid basic catalyst includes dibutyl-aniline and alkali metal compounds.
  • the alkali metal compounds includes, for example, hydroxides of alkali metal such as lithium hydroxide, sodium hydroxide and potassium hydroxide; and oxides of alkali metals such as lithium oxide, sodium oxide and potassium oxide.
  • the aforesaid acidic catalyst includes phosphoric acid, polyphosphoric acid and silica-alumina catalyst.
  • the aforesaid noble metal catalyst includes palladium black.
  • catalyst which may be used for the above-mentioned hydrogenation, there are palladium and nickel.
  • the reaction in the presence of a basic catalyst is preferably effected at 150°C or higher and the reaction in the absence of any catalyst is preferably effected at 200°C or higher.
  • the hydrogenation is preferably effected at 50° to 80°C in the case of palladium catalyst and at 130° to 180°C in the case of nickel catalyst.
  • the structural isomerization is preferably conducted at 150°C or higher. When palladium black is used, disproportionation takes place at the same time.
  • the above-mentioned alicyclic polycarboxylic acid anhydride and 4-ketopimelic acid dilactone are incorporated so that the ratio of the former to the latter may be 95/5 to 30/70, preferably 85/15 to 40/60 by weight.
  • this ratio exceeds 95/5, the flexibility of the cured product obtained by reacting the two with the epoxy resin is lowered, and when it is less than 30/70, the cured product is flexible but is lowered in hardness and easy to be injured.
  • 4-ketopimelic acid dilactone has a melting point of 65°C. Therefore, in order to mix it efficiently with the epoxy resin and prolong the pot life of the epoxy resin composition, it is preferably used in such a state that it is liquid at ordinary temperatures. Accordingly, it is preferable that as the above-mentioned alicyclic polycarboxylic acid anhydride, one that is liquid at ordinary temperatures is used, and that the component (B) and the component (C) are previously mixed and used in the form of a liquid acid anhydride composition.
  • liquid alicyclic polycarboxylic acid anhydride and 4-ketopimelic acid dilactone are preferably incorporated so that the ratio of the former to the latter may be 65/35 by weight or more.
  • acid anhydrides other than the component (B) and the component (C) may be co-used.
  • Such acid anhydrides include dodecenylsuccinic anhydride, diisobutenylsuccinic anhydride, polyazelaic polyanhydride and succinic anhydride.
  • the amount of such acid anhydrides is preferably 10% by weight or less, particularly preferably 5% by weight or less based on the total amount of the acid anhydrides. When the amount of such anhydrides is too large, mechanical strength of the cured product obtained by reaction with the epoxy resin tends to be lowered.
  • succinic anhydride is a starting material for 4-ketopimelic acid dilactone and is often inevitably contained therein depending on the degree of purification of 4-ketopimelic acid dilactone.
  • this succinic anhydride exists in a large amount in the above-mentioned liquid acid anhydride composition, it crystallizes and deposits during storage, so that the composition becomes a heterogeneous mixture. Therefore, the succinic anhydride content of the above-mentioned liquid acid anhydride composition is preferably adjusted to 1% by weight or less.
  • methods for the purification there are distillation, extraction with an organic solvent such as chloroform.
  • epoxy resin used in this invention there can be used compounds having in the molecule two or more epoxy groups, and there may be exemplified epi-bis type epoxy resins represented by diglycidyl ether of bisphenol A; alicyclic epoxy resins represented by cyclohexene oxide derivatives; novolak type epoxy resins which are glycidyl ether compounds of phenol novolak, cresol novolak or the like.
  • component (D) compounds known as hardening accelerator, for example, tertiary amines and their salts, quaternary ammonium compounds, alkali metal alcoholates and metal salts of fatty acids.
  • hardening accelerator for example, tertiary amines and their salts, quaternary ammonium compounds, alkali metal alcoholates and metal salts of fatty acids.
  • these compounds include benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 2-ethyl-4-methylimidazole, triamylammonium phenolate, sodium hexanetriol, 1,8-diazabicyclo-[5,4,0]-undecene-7 and tin octylate.
  • the amounts to be used of the component (A), the component (B), the component (C), and the optionally used component (D) are as follows.
  • the component (B) and the component (C) are used as curing agents for the epoxy resin and are used so that the sum of their amounts may be preferably 30 to 150 parts by weight, particularly preferably 50 to 120 parts by weight per 100 parts by weight of the component (A).
  • the optionally used component (D) is used in an amount of preferably less than 5 parts by weight, particularly preferably 0.1 to 3 parts by weight per 100 parts of the epoxy resin as the component (A).
  • the epoxy resin composition of this invention may contain one or more diluents, extenders, inorganic fillers, pigments, dyes, plasticizers, organic solvents, fluidity controlling agents, antifoaming agents and flame-retardants in such a range that the effects of this invention are not lessened.
  • Epikote 828 (a trade name, mfd. by Shell Chemical Co., Ltd; an epi-bis type epoxy resin, epoxy equivalent weight 185) were added 67 parts of methylhexahydrophthalic anhydride which was liquid at ordinary temperatures and 33 parts of 4-ketopimelic acid dilactone, and they were heated to 70°C and sufficiently mixed. Thereafter, 1.0 part of 2-ethyl-4-methylimidazole was added as a hardening accelerator, and the resulting composition was heated at 120°Cfor hours and then at 150°C for 15 hours to be cured.
  • the Barcol hardness (Barcol Impressor GY 934-1) of the cured product was 38.
  • Epikote 828 the same methylhexahydrophthalic anhydride as described above which was liquid at ordinary temperatures, and the same methyltetrahydrophthalic anhydride as described above which was liquid at ordinary temperatures were used according to each of the recipies shown in Table 1, and 1.0 part of 2-ethyl-4-methylimidazole was added as a hardening accelerator. Then, the resulting composition was cured under the same conditions as in Example 1, and the thus obtained cured product was tested as in Example 1. The test results are shown in Table 1.
  • the cured products of the epoxy resin compositions of this invention are excellent in all of tensile strength, elongation and hardness (Examples 2 to 5).
  • the epoxy resin alone was used, the elongation was low (Comparative Example 1), and in the case of the combination of the epoxy resin and only 4-ketopimelic acid dilactone, the elongation was high but the tensile strength and the hardness are low (Comparative Example 2).
  • the cured products obtained by using methylhexahydrophthalic anhydride and methyltetrahydrophthalic anhydride which are liquid at ordinary temperatures have low elongation values (Comparative Examples 3 and 4).
  • Example 6 In exactly the same manner as in Example 6 except that the 4-ketopimelic acid dilactone containing 0.5% by weight of succinic anhydride was replaced by polyazelaic polyanhydride (m.p. 56°C), a cured product was produced and then subjected to the tensile tests. As a result thereof, the elongation was 9.7%. The tensile strength was 657 bar. The Barcol Hardness was 16.
  • liquid acid anhydride is the component imparting flexibility to the cured articles.
  • the aforesaid methylhexahydrophthalic anhydride which was liquid at ordinary temperatures was a mixture of 70% by weight of 4-methylhexahydrophthalic anhydride which was liquid at ordinary temperatures and was obtained by hydrogenating 4-methyl-Ll 4- tetrahydrophthalic anhydride at 150°C in the presence of Raney nickel catalyst and 30% by weight of 3-methylhexahydrophthalic anhydride which was liquid at ordinary temperatures and was obtained by hydrogenating 3-methyl-0 4- tetrahydrophthalic anhydride in the same manner as described above.
  • methyltetrahydrophthalic anhydride which was liquid at ordinary temperatures was obtained by heating a mixture of 61 % by weight of 4-methyl-Ll4-tetrahydrophthalic anhydride and 39% by weight of 3-methyl-Ll4-tetrahydrophthalic anhydride at 190°C for 3 hours in the presence of polyphosphoric acid.
  • the epoxy resin composition of this invention gives a cured product excellent in elongation and tensile strength without lowering the hardness. Therefore, when the composition is used as a casting resin, particularly when an electronic part or the like is encapsulated with the composition, formation of cracks and stress placed on a semiconductor can be reduced remarkably, so that the reliability is improved. Also when the composition is used as an adhesive, warping and distortion are reduced.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Sealing Material Composition (AREA)
  • Adhesives Or Adhesive Processes (AREA)
EP83109409A 1982-09-21 1983-09-21 Epoxy resin composition Expired EP0106206B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP57164423A JPS5953527A (ja) 1982-09-21 1982-09-21 エポキシ樹脂組成物
JP164423/82 1982-09-21

Publications (2)

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EP0106206A1 EP0106206A1 (en) 1984-04-25
EP0106206B1 true EP0106206B1 (en) 1988-03-16

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US (1) US4507460A (enrdf_load_stackoverflow)
EP (1) EP0106206B1 (enrdf_load_stackoverflow)
JP (1) JPS5953527A (enrdf_load_stackoverflow)
DE (1) DE3376004D1 (enrdf_load_stackoverflow)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1334099C (en) * 1988-03-23 1995-01-24 Pen Chung Wang 1,6-diazaspiro(4,4)nonane-2,7-dione derivatives
US5057590A (en) * 1990-03-29 1991-10-15 The United States Of America As Represented By The Secretary Of The Navy Bislactone curing agents for epoxy resins and polymers obtained therefrom

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE617540A (enrdf_load_stackoverflow) * 1961-05-12

Also Published As

Publication number Publication date
JPS6224004B2 (enrdf_load_stackoverflow) 1987-05-26
DE3376004D1 (en) 1988-04-21
JPS5953527A (ja) 1984-03-28
US4507460A (en) 1985-03-26
EP0106206A1 (en) 1984-04-25

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